Oxyimino-substituted (1R,cis)-cyclopropanecarboxylate pesticides

ABSTRACT

(1R,cis)-cyclopropane compounds, substantially free of other stereoisomers, and having the formula ##STR1## wherein R is the residue of certain alcohols; and 
     R 1  is hydrogen, or certain optionally halogenated hydrocarbyl groups, are highly active pesticides.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of Ser. No. 911,743, filedJune 2, 1978, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention is directed to new oxyimino-substituted compounds, theiruse as pesticides, to pesticidal formulations containing these newcompounds and to certain novel intermediates.

2. Description of the Prior Art

U.S. Pat. No. 3,922,269 describes a class of2,2-dimethyl-3-(oxyiminomethyl)cyclopropanecarboxylic acid esters usefulas insecticides. In the case of such esters of α-substituted asymmetricalcohols, three asymmetric centers and one oxime double bond are presentand therefore a total of sixteen theoretical stereoisomers are possible.Eight theoretical stereoisomers are possible when there is no asymmetriccenter in the alcohol moiety. The above-mentioned patent states thatesters, in which the two hydrogen atoms on the cyclopropane ring are inthe absolute stereochemical relationship equivalent to that in(+)-trans-chrysanthemic acid, tend to be among the most insecticidallyactive of the various isomers and are preferred for that reason. Indeed,only (1R,trans)-cyclopropanecarboxylate oximes were apparently preparedand tested, and form the basis of the working examples.

SUMMARY OF THE INVENTION

It has now been found that certain oxyimino-substitutedcyclopropanecarboxylates derived from the (1R,cis)-form of2,2-dimethyl-3-formyl-cyclopropanecarboxylic acid are useful pesticides(insecticides and acaricides) and exhibit high knockdowncharacteristics.

Therefore, this invention is directed to new (1R,cis)-cyclopropanecompounds, substantially free of other stereoisomers, and having theformula ##STR2## wherein R¹ represents a hydrogen atom, an alkyl groupcontaining from 1 to 10 carbon atoms optionally substituted by one ormore halogen atoms, a (cycloalkyl)alkyl group containing from 3 to 7ring carbon atoms, a total of from 4 to 9 carbon atoms and optionallyring-substituted by one or more halogen atoms, a cycloalkyl groupcontaining from 3 to 7 ring carbon atoms, an alkenyl group containingfrom 3 to 4 carbon atoms optionally substituted by one or more halogenatoms or alkynyl group containing from 3 to 4 carbon atoms or an arylgroup containing from 6 to 12 carbon atoms or an aralkyl groupcontaining from 7 to 10 carbon atoms, each optionally ring-substitutedby one or more halogen atoms; and R represents a group of the formula##STR3## wherein Y represents hydrogen or an alkyl, alkenyl or alkynylgroup or an aryl or furyl group which is unsubstituted or substituted inthe ring by one or more alkyl, alkenyl, alkoxy or halogeno groups, R⁷and R⁸, which may be the same or different, each represent hydrogen oran alkyl or alkenyl group, R⁹ represents hydrogen or a methyl group, R¹⁰and R¹¹ represent hydrogen or an alkyl group, R¹² represents an organicradical having carbon-carbon unsaturation in a position α to the CH₂group to which R¹² is attached, A/S indicates an aromatic ring or adihydro or tetrahydro analogue thereof, X¹, X², X³ and X⁴, which may bethe same or different, each represents hydrogen, halogen or a methylgroup, D represents H, --CN, --C.tbd.CH or ##STR4## in which R¹³ and R¹⁴may be the same or different, each represent a hydrogen atom or an alkylgroup containing from 1 to 10 carbon atoms, Z represents --CH₂ --,--O--, --CO-- or --S--, with the proviso that when D is --CN, --C.tbd.CHor ##STR5## then the alcohol moiety is in the R,S-racemic or in theS-optical configuration.

In the above-formulas, suitable halogen atoms substituents are chlorine,fluorine or bromine.

Since the biological activity of various optical or geometric isomersand diastereoisomer pairs within the (1R,cis)esters of the invention maydiffer somewhat, it may be desirable to use a more active optical and/orgeometric isomer or diastereoisomer pair of the invention substantiallyfree of the other isomers or pair.

The oxime substituent group of the compounds of the invention gives riseto geometric isomerism by virtue of the presence of an asymmetricallysubstituted double bond. These isomers are usually described as follows:##STR6##

It should be noted that compounds wherein R¹ is haloalkyl,(cycloalkyl)alkyl optionally substituted by halogen, haloalkenyl,alkynyl, aryl optionally substituted by halogen, or aralkyl optionallysubstituted by halogen are also novel in the (1R,trans) or racemic formas for example 5-benzyl-3-furylmethyl(1R,trans)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylate,5-benzyl-3-furylmethyl(1R,trans)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)cyclopropanecarboxylateand 5-benzyl-3-furylmethyl(1R,trans)-2,2-dimethyl-3-((cyclopentoxyimino)methyl)cyclopropanecarboxylate.The compounds are claimed in applicants' co-pending application K-3219J.

The (1R,cis) esters of the present invention wherein R represents agroup of formula I, II, III, IV, V, or VI above are pesticidally active.

When the (1R,cis) ester is one formally derivable from a furylmethylalcohol, it is preferred that the furylmethyl alcohol be a 3-furylmethylalcohol as described and claimed in U.S. Pat. No. 3,466,304.

In the furylmethyl alcohols (R is formula I), and particularly in the3-furylmethyl alcohols, it is preferred that R⁷ and R⁸ each representhydrogen or groups containing up to 4 carbon atoms, particularly amethyl group and that Y represents a phenyl group which is unsubstitutedor substituted in the ring by a group containing up to 4 carbon atoms,e.g., methyl or methoxy, or by chlorine and Z is CH₂ and D is H.Analogues of these compounds where Z is O, S or CO and D is CN orC.tbd.CH are also of interest. Further compounds of interest are thosewhere Y represents a hydrogen atom, an alkyl group containing up to 4carbon atoms, an alkenyl group containing up to 4 carbon atoms, e.g.,vinyl, an alkadienyl group containing at least 4 carbon atoms or analkynyl group, e.g., propargyl, or a furyl group.

Specific alcohols of this category, from which the (1R,cis) esters ofthe invention are formally derivable, include 5-benzyl-3-furylmethylalcohol, 5-benzyl-2-methyl-3-furylmethyl alcohol,4-benzyl-5-methyl-2-furylmethyl alcohol,5-(p-methylbenzyl)-3-furylmethyl alcohol, 2,4,5-trimethyl-3-furylmethylalcohol, 4,5-dimethyl-2-furylmethyl alcohol, 5-phenoxy- and5-benzoyl-3-furylmethyl alcohol, and α-cyano substituted 5-benzyl-,5-benzoyl- or 5-phenoxy-3-furylmethyl alcohol.

The cyclopentenolones (II) from which the (1R,cis) esters of theinvention are formally derivable are those unsubstituted in the3-position or those substituted in the 3-position by a methyl group (R⁹=H or CH₃).

The cyclopentenolones (R is formula II) unsubstituted in the 3-positionare described and claimed in U.S. Pat. No. 3,720,703.

Some of these alcohols are the 3-desmethyl analogues of the alcoholsfrom which the naturally occurring pyrethrins are derived. In thepresent invention, it is preferred that R¹⁰ and R¹¹ each representhydrogen, methyl or ethyl and R¹² represents an aryl group such as aphenyl group or a phenyl group substituted by a halogeno or alkyl oralkoxy substituent of 1 to 4 carbon atoms, for example tolyl, xylyl,p-chlorophenyl or p-methoxyphenyl. R¹² may also represent a 2- or3-furyl group or an alkenyl group such as vinyl, 1-propenyl or1,3-butadienyl group.

When the (1R,cis) esters of the invention are formally derivable fromthe cyclopentenolones which are substituted in the 3-position by themethyl group (R⁹ =methyl), the (1R,cis) esters may be derived fromallethrolone (R¹⁰ =R¹¹ =H, R¹² =vinyl), pyrethrolone (R¹⁰ =R¹¹ =H, R¹²=1,3-butadienyl), cinerolone (R¹⁰ =R¹¹ =H, R¹² =1-propenyl), jasmolone(R¹⁰ =R¹¹ =H, R¹² =1-butenyl), or furethrolone (R¹⁰ =R¹¹ =H, R¹²=2-furyl).

When the (1R,cis) esters of the invention are phthalimido-methyl esterswhere R is of formula III, they may be phthalimido-,dihydrophthalimido-, or tetrahydrophthalimido-methyl esters where thephthalimido, dihydrophthalimido or tetrahydrophthalimido residue (R isformula III) is one described in British Pat. Specifications Nos.985,006, 1,052,119 or 1,058,309. 3,4,5,6-Tetrahydrophthalimidomethylesters are of particular interest.

Variations in activity, of course, depend on the individual combinationsof R and R¹ and are somewhat dependent on the susceptibility of anindividual pest to certain structural subtleties in the variouscombinations of R and R¹.

Typical examples of species within the scope of the invention are:

α-ethynyl-5-benzyl-3-furylmethyl(1R,cis)-2,2-dimethyl-3-((sec-butoxyimino)methyl)-cyclopropanecarboxylate

phthalimidomethyl(1R,cis)-2,2-dimethyl-3-((propargyloxyimino)methyl)-cyclopropanecarboxylate

3,4,5,6-tetrahydrophthalimidomethyl(1R,cis)-2,2-dimethyl-3-((isobutoxyimino)methyl)-cyclopropanecarboxylate

3-allyl-2-methyl-4-oxo-2-cyclopenten-1-yl(1R,cis)-2,2-dimethyl-3-(trifluoromethoxyimino)methyl-cyclopropanecarboxylate

3-(2-butenyl)-2-methyl-4-oxo-2-cyclopenten-1-yl(1R,cis)-2,2-dimethyl-3-((p-chlorophenoxyimino)methyl)cyclopropanecarboxylate

3,4,5,6-tetrahydrophthalimidomethyl(1R,cis)-2,2-dimethyl-3-((1-(cyclopropyl)ethoxyimino)methyl)cyclopropanecarboxylate

5-xylyl-3-furylmethyl(1R,cis)-2,2-dimethyl-3-((2-chloroethoxyimino)methyl)-cyclopropanecarboxylate

2,4,5-trimethyl-3-furylmethyl(1R,cis)-2,2-dimethyl-3-((1-cyclopropyl)ethoxyimino)methyl)-cyclopropanecarboxylate

3,6-dihydrophthalimidomethyl(1R,cis)-2,2-dimethyl-3-((phenethoxyimino)methyl)-cyclopropanecarboxylate

3,6-dihydrophthalimidomethyl(1R,cis)-2,2-dimethyl-3-((neopentoxyimino)methyl)-cyclopropanecarboxylate

5-benzyl-3-furylmethyl(1R,cis)-2,2-dimethyl-3-(cyclopropylmethoxyimino)methyl-cyclopropanecarboxylate

Because of their pesticidal utility in agricultural and domesticsituations, preferred compounds of the invention (subject to the sameprovisions stated above) are those wherein R is 5-benzyl-3-furylmethyl,α-cyano-3-phenoxybenzyl, 3-phenoxybenzyl or α-ethynyl-3-phenoxybenzyland R¹ is an alkyl group containing from 1 to 6 carbon atoms, a(cycloalkyl)alkyl group containing from 3 to 6 ring carbon atoms, atotal of from 4 to 8 carbon atoms and optionally ring-substituted byfrom 1 to 4 chlorine, fluorine and/or bromine atoms, a cycloalkyl groupcontaining from 3 to 6 ring carbon atoms, an alkenyl group containingfrom 3 to 4 carbon atoms optionally substituted by one or two chlorine,fluorine and/or bromine atoms or an alkynyl group containing from 3 to 4carbon atoms, an aryl group containing from 6 to 12 carbon atoms or anaralkyl group containing from 7 to 10 carbon atoms.

In the pesticidal (1R,cis) esters of the invention, R¹ preferablyrepresents an alkyl group containing 2 to 6 carbon atoms, such as ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, amyl,isoamyl, tert-amyl, n-hexyl and the like, a (cycloalkyl)alkyl groupcontaining from 3 to 6 ring carbon atoms and a total of from 4 to 8carbon atoms, such as cyclopropylmethyl, 1-(cyclopropyl)ethyl,cyclohexylmethyl and the like, a cycloalkyl group containing 3 to 6 ringcarbon atoms, such as cyclopropyl, cyclobutyl cyclopentyl or cyclohexyland the like, an alkenyl or alkynyl group containing 3 to 4 carbon atomssuch as allyl or propargyl and the like, an aryl group containing from 6to 10 carbon atoms such as phenyl or an aralkyl group containing from 7to 10 carbon atoms, such as benzyl, phenethyl or the like.

Preferred because of their pesticidal properties are those (1R,cis)esters wherein R¹ is an alkyl group containing from 2 to 6 carbon atoms,a (cycloalkyl)alkyl or cycloalkyl group containing 4 or 5 carbon atoms,allyl, phenyl or benzyl. Particularly suitable are those compoundswherein R¹ is an alkyl, (cyclopropyl)alkyl or cycloalkyl groupcontaining 4 or 5 carbon atoms, particularly n-butyl, isobutyl,tert-butyl, n-pentyl, cyclopentyl, (cyclopropyl)methyl or neopentyl.

Because of their useful pesticidal properties, one preferred class of(1R,cis) esters of the invention comprise those compounds wherein R¹ is(cycloalkyl)alkyl and R is one of the groups of formulas I-VI.Particularly preferred are (1R,cis) esters wherein R¹ is neopentyl,cyclopropylmethyl or cyclobutylmethyl and R is 5-benzyl-3-furylmethyl orindividual stereoisomers of such (1R,cis) esters.

The pesticidal (1R,cis) esters of the present invention may be preparedby esterification involving the reaction of an alcohol or derivativethereof of formula RQ e.g., of formula VII or VIII, and a(1R,cis)-cyclopropane carboxylic acid or derivative thereof formula IX##STR7## where Q and COP are functional groups or atoms which will reactto form an ester linkage and R, R¹, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², D, Z andY are as defined above.

It is usually convenient in practice either to treat the acid or acidhalide with the alcohol (COP=COOH or CO-halide and Q=OH) or to treat ahalogeno compound (Q=halogen) with a salt of the carboxylic acid(COP=COO--M where M is, for example, a silver or triethylammoniumcation).

Transesterification is not always practical and, it is useful to preparethe intermediate (1R,cis) alkyl ester as a tert-butyl ester(R=tert-butyl) which can be selectively converted (under acidconditions) to give the free acid which can, after conversion to theacid halide, be esterified to a pesticidal (1R,cis) ester.

Suitable routes to the (1R,cis) esters in which D is ##STR8## aresimilar to those described in Belgian Pat. No. 839,360. One routeinvolves treating the corresponding nitrile (D is --CN) with hydrogensulfide in the presence of a basic catalyst, preferably in the presenceof a solvent. Useful solvents are lower alkanols, pyridine, orpreferably a dipolar aprotic solvent, such as dimethylformamide orhexamethylphosphoramide. The catalyst is preferably a strongnitrogeneous base, particularly a tertiary amine such as triethylamine,trimethylamine, or the like, or an alkanolamine, such as triethanolamineand the like. The reaction can be carried out at room temperature. It isdesirable that the reaction solution be saturated with hydrogen sulfide.

The (1R,cis) alkyl esters of the present invention can also be preparedby treating an ester of (1R,cis)-caronaldehyde of formula ##STR9## whereR is an alkyl group, with hydroxylamine or an O-substitutedhydroxylamine of formula R¹ ONH₂ where R¹ is as defined above, and inthe case where R¹ represents hydrogen, subsequently hydrocarbylating theresulting oxime, if desired, with an alkyl (or alkenyl) halide or thelike, to give an alkoxime (or alkenyloxime), etc. Oxime formation cantake place by treating substantially equimolar amounts of aldehyde andhydroxylamine or hydrocarbyloxyamine in a polar solvent such as analkanol, e.g., ethanol or dioxane. When the aldehyde is converted intothe oxime by reaction with hydroxylamine and it is desired to convertthe resulting oxime into an alkylated or alkenylated derivative or thelike, this reaction may be carried out by procedures customarily usedfor the alkylation of phenols. Thus, the oxime may be treated in a polarsolvent, such as ethanol, with an alkyl halide, typically the bromide,in the presence of a hydrogen halide acceptor and the mixture heateduntil reaction is complete.

Oxime formation is normally carried out using an acid addition salt ofhydroxylamine or the hydrocarbyloxyamine, e.g., the hydrochloride. Inthe cases where it is desired to prepare a (1R,cis) compound where R¹represents methyl, the availability of methoxylamine hydrochloride makesit generally more convenient to carry out the reaction in one step usingmethoxylamine hydrochloride, but when compounds are required where R¹represents a larger group, it is usually more convenient to form theoxime first and subsequently to hydrocarbylate the oxime. Severalanalogs cannot be prepared by alkylation of the .tbd.NOH; e.g.,neopentyl and t-butyl.

Alcohols and halides of formula VII are described and claimed in U.S.Pat. No. 3,720,703.

Alternatively, in another modification, the compounds of the inventionare prepared by treating (1R,cis)-caronaldehydic acid previouslydescribed in U.S. Pat. No. 3,723,469 and having the formula ##STR10##with an O-substituted hydroxylamine salt of the formula R¹ ONH₃ --Wwherein R¹ is as defined above and W is the anion of salt-forminginorganic acid. Suitable inorganic acids include hydrohalogenic acidssuch as hydrochloric and hydrobromic, sulfur acids such as sulfuric, andphosphorous acids such as phosphoric. Organic acids, such as oxalic acidand the like, are also suitable to form salts.

The reaction is preferably conducted in an aqueous medium in thepresence of a buffer, such as an alkali metal salt of a polybasic acid,including sodium hydrogen carbonate, potassium hydrogen tartrate,disodium hydrogen phosphate and the like. Generally, at least one moleof buffer is used for each mole of (1R,cis)-caronaldehydic acid.

The molar ratio of reactants is not critical and can be widely varied,generally a molar ratio of the O-substituted hydroxylamine salt to(1R,cis)-caronaldehydic acid is suitably from about 1.0 to about 1.5 andpreferably from about 1.02 to about 1.3.

The reaction is generally conducted in the liquid phase by agitating,e.g., stirring, a mixture of the reactants. The resulting product isrecovered by conventional techniques such as filtering, extracting orthe like.

The reaction temperature is not critical and can easily range fromambient to the reflux temperature of any solvent employed at normalpressure. Generally, the temperature is between about 0° C. to about 50°C.

A minor amount of co-solvent can be used in the reaction medium.Suitable co-solvents are lower alcohols containing from 1 to 6 carbonatoms, such as methanol, ethanol and the like.

The resulting (1R,cis)-acids are converted to the ester compounds of theinvention, for example, by reaction with the arylmethyl halide, in thepresence of triethylamine, in a solvent, such as refluxing ethylacetate.

An isomer mixture of the (1R,cis) esters of the invention are readilyseparated into the individual diastereoisomers using known procedures,as for example, by preparative scale liquid chromatography. One suchchromatographic system which can be employed has the followingcharacteristics:

Column--porisil polar bonded phase, 9.2×250 mm

Mobile Phase--8% v/v diethyl ether in n-hexane

Flow Rate--2.5 ml/min

Detection--UV₂₅₄ at 2.0 AUFS

Injection--typically 500 ml of a 20 mg/ml solution in the mobile phase.

Such a procedure readily yields the single diastereoisomers in greaterthan 90% purity (as determined by NMR analysis). In the case of (1R,cis)esters of α-substituted alcohols four diastereoisomers are obtained.

The invention includes, within its scope, pesticidal compositionscomprising a pesticidally acceptable adjuvant--that is, at least onecarrier or a surface-active agent--and, as active ingredient, at leastone pesticidally active (1R,cis) ester of this invention. Likewise, theinvention includes also a method of combatting insect, acarine or otherarthropod pests at a locus which comprises applying to the pests or tothe locus a pesticidally effective amount of at least one compound ofthe invention.

With respect to the spectrum of pesticidal activity, the compounds ofthis invention exhibit a selective or non-selective activity on suchorders as Coleoptera, Lepidoptera (especially larvae), Diptera,Orthoptera, Hemiptera, Homoptera and Acarina depending upon a specificcombination of acid and an alcohol according to the present invention.The compositions according to the present invention are very useful forcontrolling disease carrying insects such as mosquitoes, flies andcockroaches, grain insects such as rice weevil (Sitophilus oryzae) andmites as well as agricultural noxious insects such as plant-hoppers,green rice leafhopper (Nephotettix bipuntatus cinticeps Uhler),diamond-back moths (Plutella maculipennis Curtis), imported cabbage worm(Pieris rapae Linne), rice stem borers (Chilo suppressalis Walker), cornearworm larvae (Heliothis zea Boddie), aphids, tortrixes, leaf-minersand the like.

The (1R,cis) esters are used for harvested crops, horticulturalapplication, forests, cultures in green house, and packaging materialsfor foodstuffs, household applications and as ectoparasiticides.

The term "carrier" as used herein means a material, that may beinorganic or organic and of synthetic or natural origin with which theactive compound is mixed or formulated to facilitate its application tothe plant, seed, soil and other object to be treated, or its storage,transport or handling. The carrier may be a solid or a liquid.

Suitable solid carriers may be natural and synthetic clays andsilicates, for example, natural silicas such as diatomaceous earths;magnesium silicates, for example, talcs; magnesium aluminum silicates,for example, attapulgites and vermiculites; aluminum silicates, forexample, kaolinites, montmorillonites and micas; calcium carbonate;calcium sulfate; synthetic hydrated silicon oxides and synthetic calciumor aluminum silicates; elements such as for example, carbon and sulfur;natural and synthetic resins such as, for example, coumarone resins,polyvinyl chloride and styrene polymers and copolymers; solidpolychlorophenols; bitumen, waxes such as beeswax, paraffin wax, andchlorinated mineral waxes; degradable organic solids, such as groundcorn cobs and walnut shells; and solid fertilizers, for examplesuperphosphates.

Suitable liquid carriers include solvents for the compounds of thisinvention and liquids in which the toxicant is insoluble or onlyslightly soluble.

Examples of such solvents and liquid carriers, generally, are water,alcohols, for example, isopropyl alcohol, ketones, such as acetone,methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers;aromatic hydrocarbons such as benzene, toluene and xylene; petroleumfractions, such as kerosene, light mineral oils, chlorinatedhydrocarbons, such as methylene chloride, perchlorethylene,trichloroethane, including liquified normally vaporous gaseouscompounds. Mixtures of different liquids are often suitable.

If used, the surface-active agent may be an emulsifying agent or adispersing agent or a wetting agent. It may be nonionic, ionic orpreferably, mixtures of both. Surface-active agents usually applied informulating pesticides may be used. Examples of such surface-activeagents are the sodium or calcium salts of polyacrylic acids and ligninsulfonic acids; the condensation products of fatty acids or aliphaticamines or amides containing at least 12 carbon atoms in the moleculewith ethylene oxide and/or propylene oxide; fatty acid esters ofglycerol, sorbitan, sucrose or pentaerythritol; fatty acids salts of lowmolecular weight, mono-, di- and trialkyl-amines; condensates of thesewith ethylene oxide and/or propylene oxide; condensation products offatty alcohols or alkyl phenols, for example, p-octylphenol orp-octylcresol, with ethylene oxide and/or propylene oxide; sulfates orsulfonates of these condensation products; alkali or alkaline earthmetal salts, preferably sodium salts of sulfonated castor oil, andsodium alkylaryl sulfonates such as sodium dodecylbenzene sulfonate; andpolymers of ethylene oxide and copolymers of ethylene oxide andpropylene oxide.

The compositions of the invention may be formulated as wettable powders,dusts, granules, solutions, emulsifiable concentrates, emulsions,suspension concentrates or aerosols. Encapsulated formulations andcontrolled release formulations are also contemplated, as are baitformulations. Wettable powders are usually compounded to contain 25, 50or 75% w of toxicant and usually contain, in addition to solid carrier,3-10% w of stabilizer(s) and/or other additives such as penetrants orstickers. Dusts are usually formulated as a dust concentrate having asimilar composition to that of a wettable powder but without adispersant, and are diluted in the field with further solid carrier togive a composition usually containing 1/2-10% w of toxicant. Granulesmay be manufactured by extrusion of plastics, agglomeration orimpregnation techniques. Generally, granules will contain 1/2-25% wtoxicant and 0-10% w of additives such as stabilizers, slow releasemodifiers and binding agents. Emulsifiable concentrates usually contain,in addition to the solvent, and when necessary, cosolvent, 10-50% w/vtoxicant, 2-20% w/v emulsifiers and 0-20% w/v of appropriate additivessuch as stabilizers, penetrants and corrosion inhibitors. Suspensionconcentrates are compounded so as to obtain a stable, non-sedimenting,flowable product and usually contain 10-75% w toxicant, 0-5% w ofdispersing agents, 0.1-10% w of suspending agents such as protectivecolloids and thixotropic agents, 0-10% w of appropriate additives suchas defoamers, corrosion inhibitors, stabilizers, penetrants andstickers, and as carrier, water or an organic liquid in which thetoxicant is substantially insoluble; certain organic additives orinorganic salts may be dissolved in the carrier to assist in preventingsedimentation or as antifreeze agents for water.

Aqueous dispersions and emulsions, for example, compositions obtained bydiluting a wettable powder or an emulsifiable concentrate according tothe invention with water, also lie within the scope of the presentinvention.

The compositions of the invention can also contain other ingredients,for example, other compounds possessing pesticidal, herbicidal orfungicidal properties, or attractants, such as pheromones, attractivefood ingredients, and the like, for use in baits and trap formulations.

Particularly useful compositions can be obtained by using a mixture oftwo or more kinds of the present compounds, or by the use of synergists,such as those known for use with the general class of "pyrethroid"compounds, especiallyα-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene alsoknown as piperonyl butoxide,1,2-methylenedioxy-4-[2-(octylsulfinyl)propyl]benzene,4-(3,4-methylenedioxyphenyl)-5-methyl-1,3-dioxane also known assafroxane, N-(2-ethylhexyl)bicyclo-[2,2,1]hept-5-ene-2,3-dicarboximide,octachlorodipropyl ether, isobornyl thiocyanoacetate, and othersynergists used for allethrin and pyrethrin. Useful compositions can beprepared with other biological chemicals including othercyclopropanecarboxylates, organic phosphate type insecticides andcarbamate type insecticides.

The compositions of the invention are applied in sufficient amount tosupply the effective dosage of toxicant at the locus to be protected.This dosage is dependent upon many factors, including the carrieremployed, the method and conditions of application, whether theformulation is present at the locus in the form of an aerosol, or as afilm, or as discrete particles, the thickness of film or size ofparticles, the insect or acarine species to be controlled and the like,proper consideration and resolution of these factors to provide thenecessary dosage of active material at the locus being within the skillof those versed in the art. In general, however, the effective dosage oftoxicants of this invention at the locus to be protected--i.e. theapplied dosage--is of the order or 0.01% to 0.5% based on the totalweight of the formulation, though under some circumstances the effectiveconcentration will be as little as 0.001% or as much as 2%, on the samebasis.

The superior activity of the (1R,cis) esters of the invention isusefully employed when such an ester is present in an amountsubstantially greater than that usually present in the racemate of anoxyimino substituted ester. Therefore, use of the (1R,cis) esters of theinvention in a form substantially free of other stereoisomers ispreferred, for example in a (1R,cis) isomer purity of greater than about85%, preferably in a (1R,cis) isomer purity greater than about 90% oreven greater than 95%.

ILLUSTRATIVE EMBODIMENTS

The invention is illustrated by the following embodiments which describethe preparation and biological testing of typical species of theinvention with respect to representative insects and acarines. Theembodiments are presented for the purpose of illustration only andshould not be regarded as limiting the invention in any way. Theidentity of the products, including intermediates, was confirmed byelemental, infrared and nuclear magnetic resonance spectral (NMR)analyses as necessary.

EMBODIMENT 1 5-Benzyl-3-furylmethyl(1R,cis)-2,2-dimethyl-3-((methoxyimino)methyl)cyclopropanecarboxylate

A solution of 1.6 g of (5-benzyl-3-furyl)methyl chloride and 1.3 g of(1R,cis)-2,2-dimethyl-3-(methoxyimino)methyl)cyclopropanecarboxylic acid(prepared by a method similar to that shown in Embodiment 2) and 0.8 gof triethylamine in 15 ml of ethyl acetate was refluxed for 30 hours.The resulting mixture was cooled, diluted with ether, and washed withwater. The ether phase was dried over magnesium sulfate and stripped togive an oil. This oil was chromatographed on silica gel with a mixtureof pentane-ether (6:1 ratio) as the eluant to give 1.5 g of desiredproduct as a pale yellow oil; [α]_(D) ²⁵ +5.4° (CHCl₃ ; c=0.2 g/cc).

EMBODIMENT 2(1R,cis)-2,2-dimethyl-3-((cyclopropylmethoxyimino)methyl)-cyclopropanecarboxylicacid

A solution of 1.7 g of (1R,cis)-caronaldehydic acid and 1.6 g ofcyclopropylmethoxyamine hydrochloride in 50 ml of water was stirred atroom temperature for about 4 hours in the presence of 2.2 g of sodiumbicarbonate. The resulting mixture was filtered through celite and thefiltrate was acidified to pH 4 with concentrated hydrochloric acid. Theresulting solution was extracted with methylene chloride and thecombined extracts were dried over magnesium sulfate and stripped to give2.0 g of the desired product as an oil; [α]_(D) ²⁵ +30.0° (CHCl₃ ;c=0.02 g/cc).

EMBODIMENTS 3

Procedures similar to those of Embodiments 1 and 2 were used to prepareadditional compounds of the invention shown in Table 1 below:

                  Table 1                                                         ______________________________________                                        Oxyimino-substituted (1R,cis)-Cyclopropane Derivatives                         ##STR11##                                                                    Embodi-                               [α] .sub.D.sup.25                 ment   R.sup.1     R         Isomer Z/E                                                                             (CHCl.sub.3)                            ______________________________________                                                ##STR12##  5-benzyl-3- furylmethyl                                                                 E-Z-isomers                                                                            +8.8                                    4                                                                                     ##STR13##  H         E-Z-isomers                                                                            +30.0                                   5                                                                                     ##STR14##  5-benzyl-3- furylmethyl                                                                 E-Z-isomers                                                                            +5.0                                    6      CH.sub.2 C(CH.sub.3).sub.3                                                                H         E-Z-isomers                                                                            +25.0                                   7      CH.sub.2 C(CH.sub.3).sub.3                                                                5-benzyl-3-                                                                             E-Z-isomers                                                                            -7.5                                                       furylmethyl                                                ______________________________________                                    

EMBODIMENT 8

Pesticidal Activity

Activity of the compounds of this invention with respect to insect andacarine pests was determined by using standardized test methods to testthe toxicity of the compounds as follows:

I. Houseflies (Musca domestica (Linne)) were tested by placing 50 4- to5-day old houseflies into a spray cage and spraying with 0.6 ml of asolution of test compound. After spraying, the flies were anesthetizedwith CO₂ and transferred to a recovery cage containing a milk pad forfood. The cages were held for 18-20 hours after which mortality countswere made. Both dead and moribund were counted. The tests were conductedemploying several different dosage rates of each test compound.

II. Pea aphids (Acyrthosiphon pisum (Harris)) were tested by placingabout 100 aphids on broad bean plants. The plants were sprayed withdilutions of acetone solution of test compound into water containing anemulsifier and held in containers under laboratory conditions for 18 to20 hours at which time the living aphids in the containers were counted.The tests were conducted employing several different dosage rates ofeach test compound.

III. Adult female two-spotted spider mites (Tetranychus urticae (Koch))were tested by placing 50-75 mites on the bottom side of leaves of pintobean plants. The leaves were sprayed with dilutions of acetone solutionof test compound into water containing an emulsifier and kept underlaboratory conditions for about 20 hours at which time mortality countswere made. The test were conducted employing several different dosagerates of test compounds.

IV. Mosquito larvae (Anopheles albimanus (Weide)) were tested by placingten living and active mosquito larvae in a jar containing a 0.1 mlaliquot of a 1% acetone solution of test compound thoroughly mixed with100 ml of distilled water. After 18-22 hours, mortality counts weretaken. Both dead and moribund larvae were counted as dead. Larvae whichdid not swim after being prodded with a needle were considered moribund.The tests were conducted employing several different dosage rate foreach test compound.

V. Corn earworm larvae (Heliothis zea (Boddie)) were tested by sprayinga broad bean plant with dilutions of acetone solution of test compoundinto water containing an emulsifier. Immediately after spraying, 5larvae were transferred to the plant and held for 44-46 hours, at whichtime the dead and moribund larvae were counted. The tests were conductedemploying several different dosage rates for each test compound.

In each instance, the toxicity of the compound of the invention wascompared to that of a standard pesticide (Parathion), its relativetoxicity then being expressed in terms of the relationship between theamount of compound of the invention and the amount of the standardpesticide required to produce the same percentage (50) of mortality inthe test insects or acarine. Assigning the standard pesticide anarbitrary rating of 100, the toxicities of the compounds of theinvention were expressed in terms of the toxicity indexes, whichcompares the toxicity of the compounds of the invention with that of thestandard pesticide. That is to say, a test compound having a ToxicityIndex of 50 would be half as active, while one having a Toxicity Indexof 200 would be twice as active as the standard pesticide.

Results of the above tests are shown in Table 2.

It can be seen that the compounds of the invention exhibit toxicityagainst the various pests tested and were particularly effective on cornearworm larvae. Moreover, a number of compounds of the invention areparticularly effective for controlling acarines, such as the two-spottedspider mites as indicated by the compound having a Toxicity Indexagainst mites of about 100 or greater.

                  Table 2                                                         ______________________________________                                        PESTICIDAL ACTIVITY OF (1R,CIS) CYCLOPROPANE-                                 CARBOXYLATE OXIMES EXPRESSED AS TOXICITY                                      INDEX RELATIVE TO THAT OF PARATHION                                           AS A STANDARD EQUAL TO 100                                                             House   Pea     2-Spotted                                                                            Mosquito                                                                             Corn                                   Embodiment                                                                             Fly     Aphid   Mite   Larvae Earworm                                ______________________________________                                        1         65     100      5     170    330                                    3        270     190      92    490    970                                    5        120      64     230    150    300                                    7        120     170     720     59    610                                    ______________________________________                                    

Moreover, the (1R,cis) compounds of the invention have been found to beunexpectedly more active in the control of certain pests, particularlythe corn earworm larvae and mites, than the corresponding structurallymost similar (1R,trans) compounds specifically disclosed in U.S. Pat.No. 3,922,269. Examples of such esters of the2,2-dimethyl-3-((oxyimino)methyl)cyclopropanecarboxylic acid arecompared in Table 3 expressed in terms of Toxicity Index relative toparathion as a standard equal to 100.

                                      Table 3                                     __________________________________________________________________________    PESTICIDAL ACTIVITY OF 5-BENZYL-3-FURYLMETHYL 3,3-DIMETHYL-3-                 ((OXYIMINO)METHYL)CYCLOPROPANECARBOXYLATES EXPRESSED AS                       TOXICITY INDEX RELATIVE TO THAT OF PARATHION AS A STANDARD                    EQUAL TO 100                                                                      Configuration                                                                        E/Z Isomer                                                                             House                                                                             Pea  Corn 2-Spotted                                                                           Mosquito                              R.sup.1                                                                           of Acid                                                                              Content  Fly Aphid                                                                              Earworm                                                                            Mite  Larvae                                __________________________________________________________________________    --CH.sub.3                                                                        1R,cis.sup.1                                                                         55% Z isomer/                                                                           65 100  330  5     173                                              45% E isomer                                                       --CH.sub.3                                                                        1R,trans.sup.2                                                                       60% Z isomer/                                                                          320  44  140  1      76                                              40% E isomer                                                       __________________________________________________________________________     .sup.1 Embodiment 1                                                           .sup.2 Compound named in Example 4 of U.S. Pat. No. 3,922,269.           

We claim:
 1. A (1R,cis)cyclopropane compound, substantially free ofother stereoisomers, of the formula ##STR15## wherein R¹ is an alkyl,(cycloalkyl)alkyl or cycloalkyl group containing from 4 to 5 carbonatoms.
 2. A compound according to claim 1 wherein R¹ is a(cycloalkyl)alkyl group containing from 4 to 5 carbon atoms.
 3. A(1R,cis)-cyclopropanecarboxylate, substantially free of otherstereoisomers, having the formula ##STR16## wherein R¹ is neopentyl,cyclobutylmethyl or cyclopropylmethyl.
 4. A compound according to claim1 wherein R¹ is cyclopropyl-methyl.
 5. A compound according to claim 1wherein R¹ is cyclobutyl-methyl.
 6. A compound according to claim 1wherein R¹ is neopentyl.
 7. An acaricidal composition comprising anacaricidally effective amount of an oxyimino-substituted(1R,cis)cyclopropanecarboxylate according to claim 3 and at least oneagriculturally acceptable surface-active agent or carrier therefore. 8.A method of controlling pests of the order Acarina at a locus whichcomprises applying to the pests or to the locus an acaricidallyeffective amount of an oxyimino-substituted(1R,cis)cyclopropanecarboxylate according to claim
 3. 9. An acaricidalcomposition comprising an acaricidally effective amount of anoxyimino-substituted (1R,cis)-cyclopropane compound according to claim 1and at least one agriculturally acceptable surface-active agent orcarrier therefore.
 10. A method of controlling pests of the orderAcarina at a locus which comprises applying to the pests or to the locusan acaricidally effective amount of an oxyimino-substituted(1R,cis)-cyclopropane compound according to claim 1.